Positive active material

ABSTRACT

A positive active material for a rechargeable lithium battery includes a core including a compound represented by Chemical Formula 1 and a structure-stabilizing compound on a surface of the core. The structure-stabilizing compound includes an Al compound or a Co compound. Chemical Formula 1 is Li a Ni x Co y Me z M 1   k O 2−p F p  where 0.9≤a≤1.1, 0.7≤x≤0.93, 0&lt;y≤0.3, 0&lt;z≤0.3, 0≤k≤0.005, x+y+z+k=1, 0≤p≤0.005, Me is Mn or Al, and Ml is Mg, Ba, B, La, Y, Ti, Zr, Mn, Si, V, P, Mo, W, or a combination thereof.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a divisional application based on pending application Ser. No.15/487,635, filed Apr. 14, 2017, the entire contents of which is herebyincorporated by reference.

Korean Patent Application No. 10-2016-0046345, filed on Apr. 15, 2016,in the Korean Intellectual Property Office, and entitled: “PositiveActive Material for Rechargeable Lithium Battery and RechargeableLithium Battery Including Same,” is incorporated by reference herein inits entirety.

BACKGROUND 1. Field

Embodiments are directed to a positive active material for arechargeable lithium battery and a rechargeable lithium batteryincluding the same.

2. Description of the Related Art

A rechargeable lithium battery may be used as an actuating power sourcefor a mobile information terminal such as a cell phone, a laptop, asmart phone, and the like.

The rechargeable lithium battery includes a positive electrode, anegative electrode, and an electrolyte. Herein, for a positive activematerial of a positive electrode may be an oxide consisting of lithiumand a transition metal and having a structure capable of intercalatinglithium ions, for example LiCoO₂, LiMn₂O₄, LiNi_(1−x)Co_(x)O₂ (0<x<1).

As for a negative active material, various carbon-based materials suchas artificial graphite, natural graphite, and hard carbon, whichintercalate and deintercalate lithium ions.

Recently, as the mobile information terminal has been rapidly down-sizedand lightened the rechargeable lithium battery as its actuating powersource has required much higher capacity. In addition, in order to usethe rechargeable lithium battery as an actuating power source or as apower storage source for a hybrid vehicle or an electric vehicle,research on development of a battery having satisfactory high ratecapability, being rapidly charged and discharged, and having excellentcycle characteristics is actively made.

SUMMARY

Embodiments are directed to a positive active material for arechargeable lithium battery including a core including a compoundrepresented by Chemical Formula 1 and a structure-stabilizing compoundon a surface of the core. The structure-stabilizing compound includes anAl compound or a Co compound

Li_(a)Ni_(x)Co_(y)Me_(z)M¹ _(k)O_(2−p)F_(p)   [Chemical Formula 1]

wherein, 0.9≤a≤1.1, 0.7≤x≤0.93, 0<y≤0.3, 0≤z≤0.3, 0≤k≤0.005, x+y+z+k=1,0≤p≤0.005, Me is Mn or Al, and M¹ is Mg, Ba, B, La, Y, Ti, Zr, Mn, Si,V, P, Mo, W, or a combination thereof.

The structure-stabilizing compound may be Al₂O₃, Co₃O₄, Li_(a)CoO₂ wherea is 0.9 to 1.1, or a combination thereof.

The structure-stabilizing compound may be a Co compound.

The structure-stabilizing compound may be present as a layered phase oras an island shape on the surface of the core.

A content of the structure-stabilizing compound may be about 1.5 wt % toabout 3.0 wt % based on 100 wt % of the core.

A surface of the positive active material may have a layered phasecrystal structure.

In Chemical Formula 1, x may be in the range 0.8≤x≤0.9.

Embodiments are also directed to a rechargeable lithium batteryincluding a positive electrode including a positive active material asdescribed above, a negative electrode including a negative activematerial, and an electrolyte.

BRIEF DESCRIPTION OF THE DRAWINGS

Features will become apparent to those of skill in the art by describingin detail exemplary embodiments with reference to the attached drawingsin which:

FIG. 1 illustrates a schematic view showing a structure of a positiveactive material according to an embodiment.

FIG. 2 illustrates a graph showing discharge capacity results of halfcells using the positive electrodes according to Experimental Examples 1to 8.

FIG. 3 illustrates a SEM image showing the positive active materialaccording to Example 1.

FIG. 4 illustrates TEM and SAD (selected area diffraction) imagesshowing the positive active material according to Example 1.

FIG. 5 illustrates a graph showing discharge capacity results of halfcells using the positive electrodes according to Examples 1 to 3 andReference Examples 1 to 3.

FIG. 6 illustrates a graph showing room temperature cycle-lifecharacteristic results of half cells using the positive electrodesaccording to Examples 1 to 3 and Reference Examples 1 to 3.

DETAILED DESCRIPTION

Example embodiments will now be described more fully hereinafter withreference to the accompanying drawings; however, they may be embodied indifferent forms and should not be construed as limited to theembodiments set forth herein. Rather, these embodiments are provided sothat this disclosure will be thorough and complete, and will fullyconvey exemplary implementations to those skilled in the art.

A positive active material for a rechargeable lithium battery accordingto an embodiment includes a core including a compound represented byChemical Formula 1; and a structure-stabilizing compound disposed on asurface of the core and including an Al compound or a Co compound.

Li_(a)Ni_(x)Co_(y)Me_(z)M¹ _(k)O_(2−p)F_(p)   [Chemical Formula 1]

In Chemical Formula 1, 0.9≤a≤1.1, 0.7≤x≤0.93, 0≤y≤0.3, 0<z≤0.3,0≤k≤0.005, x+y+z+k=1, 0≤p≤0.005,

Me is Mn or Al, and

M¹ is Mg, Ba, B, La, Y, Ti, Zr, Mn, Si, V, P, Mo, W, or a combinationthereof.

The positive active material has a high nickel content, with x being 0.7to 0.93. For example, in Chemical Formula 1, x may be in the range,0.8≤x≤0.9.

Such a compound of Chemical Formula 1 having a high nickel content, forexample, with x being 0.7 to 0.93, may be a compound having highcapacity. The compound of Chemical Formula 1 where x is 0.7 to 0.93 mayhave a very high capacity compared with a compound having a low nickelcontent, for example, a compound where x is less than 0.7.

In Chemical Formula 1, M¹ is a doping element that substitutes some of amain element, Ni, Co, and Me constituting the positive active materialof Chemical Formula 1. Examples of M¹ may be Mg, Ba, B, La, Y, Ti, Zr,Mn, Si, V, P, Mo, or W. In addition, F is fluorine, as a doping elementthat substitutes a some of oxygen in the positive active material ofChemical Formula 1

The structure-stabilizing compound may be Al₂O₃, Co₃O₄, Li_(a)CoO₂(where a is 0.9 to 1.1), or a combination thereof. Thestructure-stabilizing compound maybe in a form of a layered structure onthe surface of the positive active material. Such astructure-stabilizing compound may improve mobility of lithium ions andin addition, may stabilize the structure of the core and thus improveinitial efficiency and cycle-life characteristics of the positive activematerial.

In addition, when a compound core having a high nickel content, that is,a compound core having x ranging from about 0.7 to about 0.93, includesunstable Ni in a higher amount than a compound core having x of lessthan 0.6 on the surface, an effect provided by the structure-stabilizingcompound may be more effectively obtained.

Among the structure-stabilizing compounds, Li_(a)CoO₂ may be formedthrough a reaction of a Co-containing precursor with Li included on thecore and even inside the core when the Co-containing precursor isdiffused into the core in the secondary heat-treating process during aprocess of manufacturing the positive active material. For example, theLi_(a)CoO₂ may be present on the surface of and/or inside the core.

When the Li_(a)CoO₂ is included as a structure-stabilizing compound, asurface layered structure may be well developed, and thus, charge anddischarge efficiency and a cycle-life may be improved.

In particular, the structure-stabilizing compound may be a Co compound,for example, Co₃O₄, Li_(a)CoO₂, or a mixture of the Co₃O₄ and theLi_(a)CoO₂. When the structure-stabilizing compound is the mixture ofthe Co₃O₄ and Li_(a)CoO₂, their mixing ratio may be in a range ofgreater than about 0 wt %: less than about 100 wt % to about 50:50. Whenthe mixing ratio of the Co₃O₄ and the Li_(a)CoO₂ is within the range, acoating process using the Co-containing precursor may be moreeffectively performed. When the structure-stabilizing compound is a Cocompound, Co is more increasingly concentrated on the surface of thepositive active material than in the core thereof, and resultantly, Nimay be less concentrated on the surface and may stabilize the surfacestructure. In addition, when lithium ions are released from the coreincluding a compound represented by Chemical Formula 1 during the chargeand discharge, Ni may be oxidized into unstable tetravalent nickel andthen, reduced to divalent nickel and thus may form NiO. The Co compoundmay suppress formation of the NiO and decrease resistance.

The structure-stabilizing compound may be present as a layered phase (acontinuous layer type) or an island shape (an non-continuous islandtype), or as both the layered phase and the island shape on the surfaceof the core. When the structure-stabilizing compound is present as thelayered phase on the surface of the core, the structure-stabilizingcompound may be more uniformly present and may provide a greater effect.

The structure-stabilizing compound may be present on the surface of thecore, and thus may reinforce the layer structure of the active materialsurface. For example, the positive active material may have a layeredphase crystal structure on the surface. When the structure-stabilizingcompound is present as a layered phase, the active material surface mayentirely have a layered phase crystal structure. When thestructure-stabilizing compound is present as an island shape, thepositive active material may have both a layered phase crystal structureand a mixed phase crystal structure. When the structure-stabilizingcompound is present as both layered phase and island shape, both alayered phase crystal structure and a mixed phase crystal structure maybe obtained.

A content of the structure-stabilizing compound may be about 1.5 wt % toabout 3.0 wt %, or, for example, about 2.0 wt % to about 3.0 wt % basedon 100 wt % of the core. When the structure-stabilizing compound isincluded within the ranges, excellent discharge capacity and cycle-lifecharacteristics, for example, room temperature cycle-lifecharacteristics may be obtained.

The positive active material according to an embodiment may be preparedby the following process.

A lithium-containing compound, a nickel-containing compound, acobalt-containing compound, and an Me-containing compound may be mixed.Additionally, an M¹-containing compound or a fluorine-containingcompound may be mixed to prepare a mixture.

The lithium-containing compound may be a lithium acetate, a lithiumnitrate, a lithium hydroxide, a lithium carbonate, a lithium acetate, ahydrate thereof, or a combination thereof. The nickel-containingcompound may be a nickel nitrate, a nickel hydroxide, a nickelcarbonate, a nickel acetate, a nickel sulfate, a hydrate thereof, or acombination thereof. The cobalt-containing compound may be a cobaltnitrate, a cobalt hydroxide, a cobalt acetate, a cobalt carbonate, acobalt sulfate, a hydrate thereof, or a combination thereof and theMe-containing compound may be an Me-containing nitrate, an Me-containinghydroxide, an Me-containing carbonate, an Me-containing acetate, anMe-containing sulfate, a hydrate thereof, or a combination thereof. TheNV-containing compound may be an NV-containing nitrate, an NV-containinghydroxide, an NV-containing carbonate, an NV-containing acetate,NV-containing oxide, an NV-containing sulfate, and thefluorine-containing compound may be a fluorine-containing nitrate, afluorine-containing hydroxide, a fluorine-containing carbonate, afluorine-containing acetate, a fluorine-containing sulfate, afluorine-containing oxide, a hydrate thereof, or a combination thereof.

A mixing ratio of the lithium-containing compound, the nickel-containingcompound, the cobalt-containing compound, the Me-containing compound,the NV-containing compound, and the fluorine-containing compound mayappropriately be controlled such that the compound of Chemical Formula 1may be obtained.

The mixture may be subject to a primary heat-treatment to prepare acore. The primary heat-treating process may be performed at about 700°C. to about 1000° C., for about 3 hours to about 20 hours. The primaryheat-treating process may be performed under an oxygen O₂ atmosphere, orair atmosphere.

The surface of the core may be coated with a precursor of astructure-stabilizing compound. The precursor of a structure-stabilizingcompound may be Al(OH)₃, Co(OH)₃, Al₂O₃, Co₃O₄, or a combinationthereof.

The coating process may be performed in a wet process using a solvent orin a dry process without solvent. The solvent for the wet process mayinclude water, ethyl alcohol, or isopropyl alcohol.

In a process of coating a precursor of a structure-stabilizing compoundon the surface of the core, the precursor of a structure-stabilizingcompound may be mixed in an amount of about 1.5 wt % to about 3.0 wt %based on 100 wt % of the core.

After the coating process, a secondary heat-treating process may beperformed to prepare a positive active material. The secondaryheat-treating process may be performed at about 500° C. to about 800° C.for about 5 hours to about 20 hours. When the secondary heat-treatingprocess is performed within the temperature and time ranges, a compoundfor forming the structure-stabilizing compound may be well diffused ontothe surface of the core and may well form the structure-stabilizingcompound on the surface of the core.

When Al(OH)₃ is used as a precursor of a structure-stabilizing compound,an Al₂O₃ structure-stabilizing compound may be formed according to thesecondary heat-treating process. When Co(OH)₃ is used as a precursor ofa structure-stabilizing compound, a part of Co(OH) may be diffusedinside the core according to the secondary heat-treating process, andmay react with Li included in the core such that Li_(a)CoO₂ may beformed inside the core.

Another embodiment provides a rechargeable lithium battery including thepositive electrode including a positive active material, a negativeelectrode including a negative active material, and an electrolyte.

The positive electrode may include a positive active material layer anda current collector supporting the positive active material. In thepositive active material layer, a content of the positive activematerial may be about 90 wt % to about 98 wt % based on the total amountof the positive active material layer.

In an embodiment, the positive active material layer may further includea binder and a conductive material. The binder and the conductivematerial may each be included in an amount of about 1 wt % to about 5 wt%, respectively, based on the total amount of the positive activematerial layer.

The binder improves binding properties of positive active materialparticles with one another and with a current collector. Examples of thebinder may include polyvinyl alcohol, carboxymethyl cellulose,hydroxypropyl cellulose, diacetyl cellulose, polyvinylchloride,carboxylated polyvinylchloride, polyvinylfluoride, an ethyleneoxide-containing polymer, polyvinylpyrrolidone, polyurethane,polytetrafluoroethylene, polyvinylidene fluoride, polyethylene,polypropylene, a styrene-butadiene rubber, an acrylatedstyrene-butadiene rubber, an epoxy resin, nylon, or the like.

The conductive material is included to provide electrode conductivity. Asuitable electrically conductive material that does not cause a chemicalchange may be used as a conductive material. Examples of the conductivematerial may be a carbon-based material such as natural graphite,artificial graphite, carbon black, acetylene black, ketjen black, acarbon fiber, or the like; a metal-based material in a form of a metalpowder or a metal fiber and including copper, nickel, aluminum, silver,or the like; a conductive polymer such as a polyphenylene derivative; ora mixture thereof.

The current collector may be Al, as an example.

The negative electrode may include a current collector and a negativeactive material layer formed on the current collector. The negativeactive material layer may include a negative active material.

The negative active material includes a material that reversiblyintercalates/deintercalates lithium ions, a lithium metal, a lithiummetal alloy, a material being capable of doping/dedoping lithium, or atransition metal oxide.

The material that can reversibly intercalate/deintercalate lithium ionsmay include a carbon material. The carbon material may be anygenerally-used carbon-based negative active material in a lithium ionrechargeable battery. Examples of the carbon material includecrystalline carbon, amorphous carbon, and mixtures thereof. Thecrystalline carbon may be non-shaped, or sheet, flake, spherical, orfiber shaped natural graphite or artificial graphite. The amorphouscarbon may be a soft carbon, a hard carbon, a mesophase pitchcarbonization product, fired coke, or the like.

Examples of the lithium metal alloy include lithium and an elementselected from Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba,Ra, Ge, Al, and Sn.

The material being capable of doping/dedoping lithium may include Si, aSi—C composite, SiO_(x) (0<x<2), a Si-Q alloy (wherein Q is an elementselected from an alkali metal, an alkaline-earth metal, a Group 13element, a Group 14 element, a Group 15 element, a Group 16 element, atransition element, a rare earth element, and a combination thereof, andis not Si), Sn, SnO₂, a Sn—R alloy (wherein R is an element selectedfrom an alkali metal, an alkaline-earth metal, a Group 13 element, aGroup 14 element, a Group 15 element, a Group 16 element, a transitionelement, a rare earth element, and a combination thereof, and is notSn), or the like. At least one of these materials may be mixed withSiO₂. The elements Q and R may be selected from Mg, Ca, Sr, Ba, Ra, Sc,Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru,Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Tl, Ge,P, As, Sb, Bi, S, Se, Te, Po, and a combination thereof.

The transition metal oxide may include vanadium oxide, lithium vanadiumoxide, or the like.

In the negative active material layer, the negative active material maybe included in an amount of about 95 wt % to about 99 wt % based on thetotal weight of the negative active material layer.

In an embodiment, the negative active material layer includes a binder,and optionally, a conductive material. The negative active materiallayer may include about 1 wt % to about 5 wt % of a binder based on thetotal weight of the negative active material layer. When the negativeactive material layer includes a conductive material, the negativeactive material layer may include about 90 wt % to about 98 wt % of thenegative active material, about 1 wt % to about 5 wt % of the binder,and about 1 wt % to about 5 wt % of the conductive material.

The binder improves binding properties of negative active materialparticles with one another and with a current collector. The binder mayinclude a non-water-soluble binder, a water-soluble binder, or acombination thereof.

The non-water-soluble binder includes polyvinylchloride, carboxylatedpolyvinylchloride, polyvinylfluoride, an ethylene oxide-containingpolymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene,polyvinylidene fluoride, polyethylene, polypropylene, polyamideimide,polyimide, or a combination thereof.

The water-soluble binder may be a rubber-based binder or a polymer resinbinder. The rubber-based binder may be selected from a styrene-butadienerubber, an acrylated styrene-butadiene rubber (SBR), anacrylonitrile-butadiene rubber, an acrylic rubber, a butyl rubber, afluorine rubber, and a combination thereof. The polymer resin binder maybe selected from an ethylenepropylene copolymer, polyepichlorohydrine,polyphosphazene, polyacrylonitrile, polystyrene, anethylenepropylenediene copolymer, polyvinylpyridine,chlorosulfonatedpolyethylene, a latex, a polyester resin, an acrylicresin, phenolic resin, an epoxy resin, polyvinyl alcohol, and acombination thereof.

When the water-soluble binder is used as a negative electrode binder, acellulose-based compound may be further used as a thickener in order toprovide viscosity. The cellulose-based compound includes one or more ofcarboxymethyl cellulose, hydroxypropylmethyl cellulose, methylcellulose, or alkali metal salts thereof. The alkali metal may be Na, K,or Li. Such a thickener may be included in an amount of about 0.1 partsby weight to about 3 parts by weight based on 100 parts by weight of thenegative active material.

The conductive material may be included to provide electrodeconductivity. Any suitable electrically conductive material that doesnot cause chemical chance may be used as a conductive material. Examplesof the conductive material include a carbon-based material such asnatural graphite, artificial graphite, carbon black, acetylene black,ketjen black, a carbon fiber, or the like; a metal-based material of ametal powder or a metal fiber including copper, nickel, aluminum,silver, or the like; a conductive polymer such as a polyphenylenederivative; or a mixture thereof.

The current collector may include one selected from a copper foil, anickel foil, a stainless steel foil, a titanium foil, a nickel foam, acopper foam, a polymer substrate coated with a conductive metal, and acombination thereof, as examples.

The electrolyte may include a non-aqueous organic solvent and a lithiumsalt.

The non-aqueous organic solvent may serve as a medium for transmittingions taking part in the electrochemical reaction of a battery.

The non-aqueous organic solvent may include a carbonate-based,ester-based, ether-based, ketone-based, alcohol-based, or aproticsolvent.

The carbonate based solvent may include dimethyl carbonate (DMC),diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropylcarbonate (MPC), ethylpropyl carbonate (EPC), methylethyl carbonate(MEC), ethylene carbonate (EC), propylene carbonate (PC), butylenecarbonate (BC), or the like. The ester-based solvent may include methylacetate, ethyl acetate, n-propyl acetate, dimethylacetate,methylpropionate, ethylpropionate, γ-butyrolactone, decanolide,valerolactone, mevalonolactone, caprolactone, or the like. Theether-based solvent include dibutyl ether, tetraglyme, diglyme,dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, or the like.The ketone-based solvent includes cyclohexanone or the like. Thealcohol-based solvent include ethyl alcohol, isopropyl alcohol, or thelike. Examples of the aprotic solvent include nitriles such as R—CN(where R is a C2 to C20 linear, branched, or cyclic hydrocarbon, adouble bond, an aromatic ring, or an ether bond), amides such asdimethylformamide, dioxolanes such as 1,3-dioxolane, sulfolanes, and thelike.

The organic solvent may be used singularly or in a mixture. When theorganic solvent is used in a mixture, the mixture ratio may becontrolled in accordance with a desirable battery performance.

The carbonate-based solvent may include a mixture with a cycliccarbonate and a linear carbonate. The cyclic carbonate and linearcarbonate may be mixed together in a volume ratio of about 1:1 to about1:9. When the mixture is used as an electrolyte, the electrolyte mayhave enhanced performance.

The organic solvent may further include an aromatic hydrocarbon-basedsolvent as well as the carbonate-based solvent. The carbonate-basedsolvent and aromatic hydrocarbon-based solvent may be mixed together ina volume ratio of about 1:1 to about 30:1.

The aromatic hydrocarbon-based organic solvent may be an aromatichydrocarbon-based compound represented by Chemical Formula 2.

In Chemical Formula 2, R₁ to R₆ are the same or different and areselected from hydrogen, a halogen, a C1 to C10 alkyl group, a haloalkylgroup, and a combination thereof.

Specific examples of the aromatic hydrocarbon-based organic solvent maybe selected from benzene, fluorobenzene, 1,2-difluorobenzene,1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,3-trifluorobenzene,1,2,4-trifluorobenzene, chlorobenzene, 1,2-dichlorobenzene,1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene,1,2,4-trichlorobenzene, iodobenzene, 1,2-diiodobenzene,1,3-diiodobenzene, 1,4-diiodobenzene, 1,2,3-triiodobenzene,1,2,4-triiodobenzene, toluene, fluorotoluene, 2,3-difluorotoluene,2,4-difluorotoluene, 2,5-difluorotoluene, 2,3,4-trifluorotoluene,2,3,5-trifluorotoluene, chlorotoluene, 2,3-dichlorotoluene,2,4-dichlorotoluene, 2,5-dichlorotoluene, 2,3,4-trichlorotoluene,2,3,5-trichlorotoluene, iodotoluene, 2,3-diiodotoluene,2,4-diiodotoluene, 2,5-diiodotoluene, 2,3,4-triiodotoluene,2,3,5-triiodotoluene, xylene, and a combination thereof.

The electrolyte may further include an additive of vinylene carbonate,an ethylene carbonate-based compound represented by Chemical Formula 3,or propanesultone to improve cycle life.

In Chemical Formula 3, R₇ and R₈ are the same or different and may beeach independently hydrogen, a halogen, a cyano group (CN), a nitrogroup (NO₂), or a C1 to C5 fluoroalkyl group, provided that at least oneof R₇ and R₈ is a halogen, a cyano group (CN), a nitro group (NO₂), or aC1 to C5 fluoroalkyl group, and R₇ and R₈ are not simultaneouslyhydrogen.

Examples of the ethylene carbonate-based compound includedifluoroethylene carbonate, chloroethylene carbonate, dichloroethylenecarbonate, bromoethylene carbonate, dibromoethylene carbonate,nitroethylene carbonate, cyanoethylene carbonate, vinylethylenecarbonate, fluoroethylene carbonate, or the like. The amount of theadditive for improving cycle life may be flexibly used within anappropriate range.

The lithium salt dissolved in an organic solvent supplies a battery withlithium ions, basically operates the rechargeable lithium battery, andimproves transportation of the lithium ions between positive andnegative electrodes. Examples of the lithium salt include at least onesupporting salt selected from LiPF₆, LiBF₄, LiSbF₆, LiAsF₆,LiN(SO₂C₂F₅)₂, Li(CF₃SO₂)₂N, LiN(SO₃C₂F₅)₂, LiC₄F₉SO₃, LiClO₄, LiAlO₂,LiAlCl₄, LiN(C_(x)F_(2x+1)SO₂)(C_(y)F_(2y+1)SO₂) (where x and y arenatural numbers, for example, integers of 1 to 20), LiCl, LiI, andLiB(C₂O₄)₂ (lithium bis(oxalato) borate; LiBOB). The lithium salt may beused in a concentration ranging from about 0.1 M to about 2.0 M. Whenthe lithium salt is included at the above concentration range, anelectrolyte may have excellent performance and lithium ion mobility dueto optimal electrolyte conductivity and viscosity.

The rechargeable lithium battery may further include a separator betweenthe negative electrode and the positive electrode, depending on a kindof the battery. Examples of a suitable separator material includepolyethylene, polypropylene, polyvinylidene fluoride, and multi-layersthereof such as a polyethylene/polypropylene double-layered separator, apolyethylene/polypropylene/polyethylene triple-layered separator, and apolypropylene/polyethylene/polypropylene triple-layered separator.

FIG. 1 illustrates an exploded partial perspective view of arechargeable lithium battery according to an embodiment. Therechargeable lithium battery may one of variously-shaped batteries suchas a cylindrical battery, a pouch battery, or the like. For example, asshown in FIG. 1, the rechargeable lithium battery may be a prismaticrechargeable lithium battery.

Referring to FIG. 1, a rechargeable lithium battery 100 according to anembodiment may include an electrode assembly 40 manufactured by windinga separator 30 interposed between a positive electrode 10 and a negativeelectrode 20, and a case 50 housing the electrode assembly 40. Anelectrolyte may be impregnated in the positive electrode 10, thenegative electrode 20, and the separator 30. The case may be sealed, forexample, by a cover or cap or other form of sealing member, depending onthe type of rechargeable lithium battery. Electrode tabs or terminalselectrically connected to the positive electrode 10 and the negativeelectrode 20, respectively, may be outside the case.

The following Examples and Comparative Examples are provided in order tohighlight characteristics of one or more embodiments, but it will beunderstood that the Examples and Comparative Examples are not to beconstrued as limiting the scope of the embodiments, nor are theComparative Examples to be construed as being outside the scope of theembodiments. Further, it will be understood that the embodiments are notlimited to the particular details described in the Examples andComparative Examples.

Experimental Example 1

Lithium carbonate, nickel sulfate, cobalt sulfate, and manganese sulfatewere mixed to have a mole ratio of Li:Ni:Co:Mn=1:0.5:0.2:0.3.

The mixture was heat-treated at 740° C. under an oxygen (O₂) atmospherefor 20 hours to prepare a LiNi_(0.5)Co_(0.2)Mn_(0.3)O₂ positive activematerial.

94 wt % of the prepared positive active material, 3 wt % of apolyvinylidene fluoride binder, and 3 wt % of a ketjen black conductivematerial were mixed or dissolved in an N-methylpyrrolidone solvent toprepare a positive active material composition. The positive activematerial composition was coated onto an Al current collector tomanufacture a positive electrode.

Experimental Example 2

A LiNi_(0.6)Co_(0.2)Mn_(0.2)O₂ positive active material was preparedaccording to the same method as Experimental Example 1 except for mixinglithium carbonate, nickel sulfate, cobalt sulfate, and manganese sulfateto have a mole ratio of Li:Ni:Co:Mn=1:0.6:0.2:0.2. The positive activematerial was used according to the same method as Experimental Example 1to manufacture a positive electrode.

Experimental Example 3

A LiNi_(0.7)Co_(0.15)Mn_(0.15)O₂ positive active material was preparedaccording to the same method as Experimental Example 1 except for mixinglithium hydroxide, nickel sulfate, cobalt sulfate, and manganese sulfateto have a mole ratio of Li:Ni:Co:Mn=1:0.7:0.15:0.15. The positive activematerial was used according to the same method as Experimental Example 1to manufacture a positive electrode.

Experimental Example 4

A LiNi_(0.8)Co_(0.15)Al_(0.05)O₂ positive active material was preparedaccording to the same method as Experimental Example 1 except for mixinglithium hydroxide, nickel sulfate, cobalt sulfate, and aluminum sulfateto have a mole ratio of Li:Ni:Co:Al=1:0.8:0.15:0.05. The positive activematerial was used according to the same method as Experimental Example 1to manufacture a positive electrode.

Experimental Example 5

A LiNi_(0.82)Co_(0.15)Al_(0.03)O₂ positive active material was preparedaccording to the same method as Experimental Example 1 except for mixinglithium hydroxide, nickel sulfate, cobalt sulfate, and aluminum sulfateto have a mole ratio of Li:Ni:Co:Al=1:0.82:0.15:0.03. The positiveactive material was used according to the same method as ExperimentalExample 1 to manufacture a positive electrode.

Experimental Example 6

A LiNi_(0.85)Co_(0.135)Al_(0.015)O₂ positive active material wasprepared according to the same method as Experimental Example 1 exceptfor mixing lithium hydroxide, nickel sulfate, cobalt sulfate, andaluminum sulfate to have a mole ratio of Li:Ni:Co:Al=1:0.85:0.135:0.015.The positive active material was used according to the same method asExperimental Example 1 to manufacture a positive electrode.

Experimental Example 7

A LiNi_(0.9)Co_(0.09)Al_(0.01)O₂ positive active material was preparedaccording to the same method as Experimental Example 1 except for mixinglithium hydroxide, nickel sulfate, cobalt sulfate, and aluminum sulfateto have a mole ratio of Li:Ni:Co:Al=1:0.9:0.09:0.01. The positive activematerial was used according to the same method as Experimental Example 1to manufacture a positive electrode.

Experimental Example 8

A LiNi_(0.92)Co_(0.07)Al_(0.01)O₂ positive active material was preparedaccording to the same method as Experimental Example 1 except for mixinglithium hydroxide, nickel sulfate, cobalt sulfate, and aluminum sulfateto have a mole ratio of Li:Ni:Co:Al=1:0.92:0.07:0.01. The positiveactive material was used according to the same method as ExperimentalExample 1 to manufacture a positive electrode.

Each positive electrode according to Experimental Examples 1 to 8, alithium metal counter electrode, and an electrolyte were used tomanufacture a coin-type half-cell in a general method. The electrolytewas prepared by dissolving 1.0 M LiPF₆ in a mixed solvent of ethylenecarbonate and diethyl carbonate (50:50 volume ratio).

The half-cell was charged and discharged at 25° C. within a range of 3.0V to 4.3 V at 0.2 C. Then, the discharge capacity of the half-cell wasmeasured. The results for Experimental Examples 1 to 8 are provided inFIG. 2. (The circles in FIG. 2 correspond to Experimental Examples 1 to8 in order, from left to right.)

As shown in FIG. 2, as a nickel content was increased, capacity wasincreased. For example, when x in a Li_(a)Ni_(x)Co_(y)Mn_(z)O₂ compoundwas greater than or equal to 0.7 (greater than or equal to 70% in FIG.2), a capacity greater than or equal to 180 mAh/g was obtained.

Example 1

Lithium hydroxide, nickel sulfate, cobalt sulfate, and aluminum sulfatewere mixed to have a mole ratio of Li:Ni:Co:Al:Ti=1:0.85:0.135:0.015.

The mixture was primarily heat-treated at 740° C. under an oxygen (O₂)atmosphere for 20 hours to prepare a LiNi_(0.85)Co_(0.135)Al_(0.015)O₂core.

The core was mixed with Co(OH)₂ in a ratio of 100 wt %:1.5 wt % in awater solvent in a wet coating process, and the mixture was secondarilyheat-treated at 700° C. under an oxygen atmosphere for 10 hours toprepare a positive active material including theLiNi_(0.85)Co_(0.135)Al_(0.015)O₂ core and a Co₃O₄ and Li_(a)CoO₂ (50:50wt %, a=1.0) structure-stabilizing compound on the surface of the core.The Co₃O₄ and Li_(a)CoO₂ structure-stabilizing compound was present asan island shape and a layered phase on the surface of the core. Inaddition, the structure-stabilizing compound was present in an amount of1.5 wt % based on 100 wt % of the core in the final positive activematerial. 94 wt % of the prepared positive active material, 3 wt % of apolyvinylidene fluoride binder, and 3 wt % of a ketjen black conductivematerial were mixed or dissolved in an N-methylpyrrolidone solvent toprepare a positive active material composition. The positive activematerial composition was coated onto an Al current collector tomanufacture a positive electrode.

Example 2

A positive active material including a core and a Co₃O₄ and Li_(a)CoO₂(50:50 wt %, a=1.0) structure-stabilizing compound on the surface of thecore was prepared according to the same method as Example 1 except formixing the LiNi_(0.85)Co_(0.135)Al_(0.015)O₂ core of Example 1 withCo(OH)₂ in a ratio of 100 wt %:2 wt %. In the final positive activematerial, the structure-stabilizing compound was present in an amount of2 wt % based on 100 wt % of the core.

A positive electrode was manufactured using the positive active materialaccording to the same method as in Example 1.

Example 3

A positive active material including a core and a Co₃O₄ and Li_(a)CoO₂(50:50 wt %, a=1.0) structure-stabilizing compound on the surface of thecore was prepared according to the same method as Example 1 except formixing the LiNi_(0.85)Co_(0.135)Al_(0.015)O₂ core of Example 1 withCo(OH)₂ in a ratio of 100 wt %:3 wt %. In the positive active material,the structure-stabilizing compound was present in an amount of 3 wt %based on 100 wt % of the core.

A positive electrode was manufactured using the positive active materialaccording to the same method as in Example 1.

Reference Example 1

A positive active material including a core and a Co₃O₄ and Li_(a)CoO₂(50:50 wt %, a=1.0) structure-stabilizing compound on the surface of thecore was prepared according to the same method as Example 1 except formixing the LiNi_(0.85)Co_(0.135)Al_(0.015)O₂ core of Example 1 withCo(OH)₂ in a ratio of 100 wt %:0.5 wt %. In the final positive activematerial, the structure-stabilizing compound was present in an amount of0.5 wt % based on 100 wt % of the core.

A positive electrode was manufactured using the positive active materialaccording to the same method as in Example 1.

Reference Example 2

A positive active material including a core and a Co₃O₄ and Li_(a)CoO₂(50:50 wt %, a=1.0) structure-stabilizing compound on the surface of thecore was prepared according to the same method as Example 1 except formixing the LiNi_(0.85)Co_(0.135)Al_(0.015)O₂ core of Example 1 withCo(OH)₂ in a ratio of 100 wt %:1 wt %. In the final positive activematerial, the structure-stabilizing compound was present in an amount of1 wt % based on 100 wt % of the core.

A positive electrode was manufactured using the positive active materialaccording to the same method as in Example 1.

Reference Example 3

A positive active material including a core and a Co₃O₄ and Li_(a)CoO₂(50:50 wt %, a=1.0) structure-stabilizing compound on the surface of thecore was prepared according to the same method as Example 1 except formixing the LiNi_(0.85)Co_(0.135)Al_(0.015)O₂ core of Example 1 withCo(OH)₂ in a ratio of 100 wt %:5 wt %. In the final positive activematerial, the structure-stabilizing compound was present in an amount of5 wt % based on 100 wt % of the core.

A positive electrode was manufactured using the positive active materialaccording to the same method as in Example 1.

Evaluation of Surface Characteristics

FIG. 3 illustrates a SEM image showing the positive active material ofExample 1. As shown in FIG. 3, the positive active material of Example 1has a Co-including structure-stabilizing compound coated as an islandshape and a layered phase on the surface of the core.

FIG. 4(a) illustrates a TEM image showing the positive active materialof Example 1, FIG. 4(b) illustrates a SAD (selected area diffraction)image showing the surface corresponding to area 1 in FIG. 4(a), and FIG.4c ) of FIG. 4 illustrates a SAD (selected area diffraction) imageshowing the surface corresponding to area 2 in (FIG. 4a ). As shown inFIGS. 4(b) and 4(c), the surface of the positive active material ofExample 1 had a layered crystal structure and a mixed crystal structure.

Evaluation of Battery Characteristics

Each positive electrode according to Examples 1 to 3 and ReferenceExamples 1 to 3, a lithium metal counter electrode, and an electrolytewere used to manufacture in a coin-type half-cell in a general method.The electrolyte was prepared by dissolving 1.3 M LiPF₆ in a mixedsolvent of ethylene carbonate and diethyl carbonate (50:50 volumeratio).

The manufactured half-cell was charged and discharged 50 times at 25° C.in a range of 3.0 V to 4.3 V at 0.2 C, and discharge capacity of thehalf-cell was measured. In addition, a capacity retention was obtainedby calculating a ratio of the 50th discharge capacity relative to thefirst discharge capacity as a cycle-life.

The results of the half-cells respectively using the positive electrodesaccording to Examples 1 to 3 and Reference Examples 1 to 3 are shown inTable 1. In addition, the discharge capacity results of the half-cellsrespectively using the positive electrodes according to Examples 1 to 3and Reference Examples 1 to 3 are shown in FIG. 5, and room temperaturecycle-life characteristic results of the half-cells are shown in FIG. 6.

TABLE 1 Content of structure- Discharge Room temperature stabilizingcompound capacity cycle-life (wt %) (mAh/g) (%) Reference 0.5 200 84Example 1 Reference 1 200 84 Example 2 Example 1 1.5 200 85 Example 2 2201 86 Example 3 3 201 87 Reference 5 199 83 Example 3

As shown in Table 1 and FIGS. 5 and 6, the half-cells respectively usingthe positive electrodes using a positive active material including Co₃O₄and Li_(a)CoO₂ as a structure-stabilizing compound in a range of 1.5 wt% to 3 wt % according to Examples 1 to 3 exhibited discharge capacity ofgreater than or equal to 200 mAh/g and cycle-life characteristics ofgreater than or equal to 85%. The half-cells including thestructure-stabilizing compound in a smaller amount than the rangeaccording to Reference Examples 1 and 2 and the half-cells including thestructure-stabilizing compound in a larger amount than the rangeaccording to Reference Example 3 exhibited deteriorated capacity andcycle-life characteristics.

Comparative Example 1

Lithium hydroxide, nickel sulfate, cobalt sulfate, and aluminum sulfatewere mixed to have a mole ratio of Li:Ni:Co:Al=1:0.85:0.135:0.015.

The mixture was subjected to a primary heat treatment at 740° C. underan oxygen (O₂) atmosphere for 20 hours to prepare aLiNi_(0.85)Co_(0.135)Al_(0.015)O₂ positive active material. A positiveelectrode was manufactured using the positive active material accordingto the same method as in Example 1.

Evaluation of Battery Characteristics (Example 1 and Comparative Example1)

Each positive electrode according to Example 1 and Comparative Example1, a lithium metal counter electrode, and an electrolyte were used tomanufacture a coin-type half-cell in a general method. The electrolytewas prepared by dissolving 1.3 M LiPF₆ in a mixed solvent of ethylenecarbonate and diethyl carbonate (50:50 volume ratio).

The half-cells were charged and discharged once at 0.1 C in a range of2.8 V to 4.4 V with a current density of 3.0 mA/cm² to perform aformation process. The charge and discharge capacities and efficienciesof the half-cells were measured, and the results are shown in Table 2.

After the formation process, the cells were charged and discharged onceat 0.2 C in a range of 2.8 V to 4.4 V with a current density of 3.0mA/cm². The discharge capacities of the half cells were measured, andthe results are shown in Table 2.

TABLE 2 Formation process 0.2 C 0.1 C charge 0.1 C discharge dischargecapacity capacity Efficiency capacity (mAh/g) (mAh/g) (%) (mAh/g)Comparative 234.9 209.1 89.0 202.8 Example 1 Example 1 235.7 212.6 90.2207.6

As shown in Table 2, the positive active material having astructure-stabilizing compound on the surface according to Example 1exhibited excellent charge and discharge characteristics compared withthe positive active material including no structure-stabilizing compoundaccording to Comparative Example 1.

Example 4

Lithium hydroxide, nickel sulfate, cobalt sulfate, and manganese sulfatewere mixed to have a mole ratio of Li:Ni:Co:Mn=1:0.85:0.135:0.015.

The mixture was subjected to a primary heat-treatment at 740° C. underan oxygen (O₂) atmosphere for 20 hours to prepare aLiNi_(0.85)Co_(0.135)Mn_(0.015)O₂ core.

The core was mixed with Co(OH)₂ in a ratio of 100 wt %:1.5 wt % in awater solvent through a wet coating process, this mixture was subjectedto a secondary heat-treatment at 700° C. under an oxygen atmosphere for10 hours to prepare a positive active material including theLiNi_(0.85)Co_(0.135)Mn_(0.015)O₂ core and a Co₃O₄ and Li_(a)CoO₂ (50:50wt %, a=1.0) structure-stabilizing compound on the surface of the core.The Co₃O₄ and Li_(a)CoO₂ structure-stabilizing compound was present asan island shape and a layered phase on the surface of the core. Inaddition, in the final positive active material, thestructure-stabilizing compound was included in an amount of 1.5 wt %based on 100 wt % of the core.

94 wt % of the prepared positive active material, 3 wt % of apolyvinylidene fluoride binder, and 3 wt % of a ketjen black conductivematerial were mixed or dissolved in an N-methylpyrrolidone solvent toprepare a positive active material composition. The positive activematerial composition was coated onto an Al current collector tomanufacture a positive electrode.

Example 5

A positive active material including a core and a Co₃O₄ and Li_(a)CoO₂(50:50 wt %, a=1.0) structure-stabilizing compound on the surface of thecore was prepared according to the same method as Example 1 except formixing the LiNi_(0.85)Co_(0.135)Mn_(0.015)O₂ core of Example 4 withCo(OH)₂ in a ratio of 100 wt %:2 wt %. In the final positive activematerial, the structure-stabilizing compound was present in an amount of2 wt % based on 100 wt % of the core.

A positive electrode was manufactured using the positive active materialaccording to the same method as in Example 1.

Example 6

A positive active material including a core and a Co₃O₄ and Li_(a)CoO₂(50:50 wt %, a=1.0) structure-stabilizing compound on the surface of thecore was prepared according to the same method as Example 1 except formixing the LiNi_(0.85)Co_(0.135)Mn_(0.015)O₂ core of Example 4 withCo(OH)₂ in a ratio of 100 wt %:3 wt %. In the final positive activematerial, the structure-stabilizing compound was present in an amount of3 wt % based on 100 wt % of the core.

A positive electrode was manufactured using the positive active materialaccording to the same method as in Example 1.

Reference Example 4

A positive active material including a core and a Co₃O₄ and Li_(a)CoO₂(50:50 wt %, a=1.0) structure-stabilizing compound on the surface of thecore was prepared according to the same method as Example 1 except formixing the LiNi_(0.85)Co_(0.135)Mn_(0.015)O₂ core of Example 4 withCo(OH)₂ in a ratio of 100 wt %:0.5 wt %. In the final positive activematerial, the structure-stabilizing compound was present in an amount of0.5 wt % based on 100 wt % of the core.

A positive electrode was manufactured using the positive active materialaccording to the same method as in Example 1.

Reference Example 5

A positive active material including a core and a Co₃O₄ and Li_(a)CoO₂(50:50 wt %, a=1.0) structure-stabilizing compound on the surface of thecore was prepared according to the same method as Example 1 except formixing the LiNi_(0.85)Co_(0.135)Mn_(0.015)O₂ core of Example 4 withCo(OH)₂ in a ratio of 100 wt %:1 wt %. In the positive active material,the structure-stabilizing compound was present in an amount of 1 wt %based on 100 wt % of the core.

A positive electrode was manufactured using the positive active materialaccording to the same method as in Example 1.

Reference Example 6

A positive active material including a core and a Co₃O₄ and Li_(a)CoO₂(50:50 wt %, a=1.0) structure-stabilizing compound on the surface of thecore was prepared according to the same method as Example 1 except formixing the LiNi_(0.85)Co_(0.135)Mn_(0.015)O₂ core of Example 4 withCo(OH)₂ in a ratio of 100 wt %:5 wt %. In the final positive activematerial, the structure-stabilizing compound was present in an amount of5 wt % based on 100 wt % of the core.

A positive electrode was manufactured using the positive active materialaccording to the same method as in Example 1.

Evaluation of Battery Characteristics (Examples 4 to 6 and ReferenceExamples 4 to 6)

Each positive electrode according to Examples 4 to 6 and ReferenceExamples 4 to 6, a lithium metal counter electrode, and an electrolytewere used to manufacture a coin-type half-cell in a general method. Theelectrolyte was prepared by dissolving 1.3 M LiPF₆ in a mixed solvent ofethylene carbonate and diethyl carbonate (50:50 of a volume ratio).

The manufactured half-cells were charged and discharged 50 times at 25°C. in a range of 3.0 V to 4.3 Vat 0.2 C, and the discharge capacities ofthe half-cells were measured. In addition, a capacity retention valuewas obtained by calculating a ratio of the 50th discharge capacityrelative to the first discharge capacity to evaluate a cycle-life.

The results with respect to the half-cells manufactured by respectivelyusing the positive electrodes according to Examples 4 to 6 and ReferenceExamples 4 to 6 were shown in Table 3.

TABLE 3 Content of structure- Discharge Room stabilizing compoundcapacity temperature (wt %) (mAh/g) cycle-life (%) Reference 0.5 200 84Example 4 Reference 1 200 84 Example 5 Example 4 1.5 201 86 Example 5 2202 87 Example 6 3 202 87 Reference 5 199 83 Example 6

As shown in Table 3, the half-cells using the positive electrodes usingthe positive active material including Co₃O₄ and Li_(a)CoO₂ in an amountof 1.5 wt % to 3 wt % as a structure-stabilizing compound according toExamples 4 to 6 showed discharge capacity of greater than or equal to200 mAh/g and cycle-life characteristics of greater than or equal to85%, while the half-cells including the structure-stabilizing compoundin a smaller amount than the range according to Reference Examples 4 and5 and the half-cells including the structure-stabilizing compound in alarger amount than the range according to Reference Example 6 exhibiteddeteriorated cycle-life characteristics.

Comparative Example 2

Lithium hydroxide, nickel sulfate, cobalt sulfate, and manganese sulfatewere mixed to have a mole ratio of Li:Ni:Co:Mn=1:0.85:0.135:0.015.

The mixture was subjected to primary heat-treatment at 740° C. under anoxygen (O₂) atmosphere for 20 hours to prepare aLiNi_(0.85)Co_(0.135)Mn_(0.015)O₂ positive active material. A positiveelectrode was manufactured using the positive active material accordingto the same method as in Example 1.

Evaluation of Battery Characteristics (Example 4 and Comparative Example2)

Each positive electrode according to Example 4 and Comparative Example2, a lithium metal counter electrode, and an electrolyte were used tomanufacture a coin-type half-cell in a general method. The electrolytewas prepared by dissolving 1.3 M LiPF₆ in a mixed solvent of ethylenecarbonate and diethyl carbonate (50:50 volume ratio).

The manufactured half-cells were charged and discharged once at 0.1 C ina range of 2.8 V to 4.4 V with a current density of 3.0 mA/cm² toperform a formation process. The charge and discharge capacities andefficiencies of the half-cells were obtained, and the results are shownin Table 4.

In addition, after the formation process, the cells were charged anddischarged once at 0.2 C in a range of 2.8 V to 4.4 V with a currentdensity of 3.0 mA/cm². The discharge capacities of the half-cells wereobtained, and the results are shown in Table 4.

TABLE 4 Formation process 0.2 C 0.1 C charge 0.1 C discharge dischargecapacity capacity Efficiency capacity (mAh/g) (mAh/g) (%) (mAh/g)Comparative 235.5 209.5 88.9 202.5 Example 2 Example 4 236.5 212.5 89.9207.5

As shown in Table 4, the positive active material having thestructure-stabilizing compound on the surface according to Example 4showed excellent charge and discharge characteristics compared with thepositive active material including no structure-stabilizing compoundaccording to Comparative Example 2.

By way of summation and review, a rechargeable lithium battery includesa positive electrode, a negative electrode, and an electrolyte. Apositive active material of a positive electrode may be an oxideincluding lithium and a transition metal and having a structure capableof intercalating lithium ions. For example, the positive active materialmay be LiCoO₂, LiMn₂O₄, or LiNi_(1−x)Co_(x)O₂ (0<x<1).

As for a negative active material, various carbon-based materials suchas artificial graphite, natural graphite, and hard carbon, whichintercalate and deintercalate lithium ions.

Recently, as mobile information terminals have been rapidly down-sizedand made lighter, it has become desirable for a rechargeable lithiumbattery as an actuating power source to have a much higher capacity. Inaddition, in order to use the rechargeable lithium battery as anactuating power source or as a power storage source for a hybrid vehicleor an electric vehicle, research on developing a battery having asatisfactory high rate capability, an ability to be rapidly charged anddischarged, and excellent cycle characteristics is being activelyconducted.

Embodiments provide a positive active material for a rechargeablelithium battery having high capacity and excellent cycle-lifecharacteristics.

Embodiment provide a rechargeable lithium battery including the positiveactive material.

Example embodiments have been disclosed herein, and although specificterms are employed, they are used and are to be interpreted in a genericand descriptive sense only and not for purpose of limitation. In someinstances, as would be apparent to one of ordinary skill in the art asof the filing of the present application, features, characteristics,and/or elements described in connection with a particular embodiment maybe used singly or in combination with features, characteristics, and/orelements described in connection with other embodiments unless otherwisespecifically indicated. Accordingly, it will be understood by those ofskill in the art that various changes in form and details may be madewithout departing from the spirit and scope thereof as set forth in thefollowing claims.

1.-8. (canceled)
 9. A positive active material formed by a processcomprising: mixing a core including a compound represented by ChemicalFormula 1 and Co(OH)₂ in a water solvent, and heat-treating the mixtureat about 500° C. to about 800° C. for about 5 to about 20 hours, therebypreparing the positive active material,Li_(a)Ni_(x)Co_(y)Me_(z)M¹ _(k)O_(2−p)F_(p)   [Chemical Formula 1]wherein, 0.9≤a≤1.1, 0.7≤x≤0.93, 0<y≤0.3, 0≤z≤0.3, 0≤k≤0.005, x+y+z+k=1,0 p≤0.005, Me is Mn or Al, and M¹ is Mg, Ba, B, La, Y, Ti, Zr, Mn, Si,V, P, Mo, W, or a combination thereof.
 10. The positive active materialas claimed in claim 9, wherein mixing the core including the compoundrepresented by Chemical Formula 1 and Co(OH)₂ includes mixing Co(OH)₂ inan amount of about 1.5 wt % to about 3 wt % based on 100 wt % of thecore.
 11. The positive active material as claimed in claim 9, whereinheat-treating the mixture is at 700° C. under an oxygen atmosphere for10 hours.
 12. The positive active material as claimed in claim 9,wherein the positive active material prepared by the process includesthe core and Co₃O₄ and Li_(a)CoO₂ on the surface of the core.